Multi-coated metallic products and methods of making the same

ABSTRACT

The present invention relates generally to a coated jewelry article or a coated component of a jewelry article, comprising a jewelry article or a component of a jewelry article, a first metallic coating, and a second metallic coating.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a Divisional of U.S. Nonprovisionalapplication Ser. No. 15/960,116 filed 23 Apr. 2018; which is aDivisional of U.S. Nonprovisional application Ser. No. 14/589,924 filed5 Jan. 2015, now U.S. Pat. No. 9,949,538 issued 24 Apr. 2018; which is aContinuation of U.S. Nonprovisional application Ser. No. 14/165,531filed 27 Jan. 2014, now U.S. Pat. No. 8,927,107 issued 6 Jan. 2015;which is a Continuation of U.S. Nonprovisional application Ser. No.13/486,081 filed 1 Jun. 2012, now U.S. Pat. No. 8,932,437 issued 13 Jan.2015; which claims the benefit of U.S. Provisional Application Ser.61/493,249 filed 3 Jun. 2011; each of which are fully incorporatedherein by reference in its entirety for all purposes.

BACKGROUND OF THE INVENTION

The present application generally relates to metal or metallic articlessuch as jewelry that are coated or plated with metal or metalliccoatings.

Plating is a process where a thin layer of metal is deposited on thesurface of a substrate. Metals are plated for various reasons, includingfor decoration, to harden, to alter conductivity, to inhibit corrosion,to reduce friction, to improve paint adhesion, to improve solderability,to improve wearability, and for radiation shielding. Gemstones can alsobe plated to provide improved color characteristics. See, e.g., U.S.Pat. No. 5,853,826.

Processes used in plating include electroplating, physical vapordeposition (PVD) and chemical vapor deposition (CVD). In electroplating,an electrical current is used to reduce cations of a coating materialfrom a solution to coat a conductive substrate with a thin layer of thematerial. In PVD, a vaporized form of the coating metal is condensed ina vacuum onto the substrate surface. Vaporization and deposition of thecoating metal can be effected by a number of methods known in the art,including evaporative deposition, electron beam physical vapordeposition, sputter deposition, cathodic arc deposition, pulsed laserdeposition, and plasma-spray deposition. CVD involves exposing thesubstrate to a volatile precursor of the coating metal, which reacts ordecomposes on the substrate surface.

While electroplating is the simplest process of plating a metal,electroplating is difficult or impossible where the substrate is arefractory metal such as tungsten, molybdenum, niobium, tantalum orrhenium. In particular, tungsten and tungsten alloys such as tungstencarbide cannot be electroplated. Thus, a tungsten or tungsten alloyarticle such as an article of jewelry cannot be directly electroplatedwith, e.g., a layer of a precious metal such as gold, platinum orrhodium. This makes production of plated articles of a tungsten ortungsten alloy substrate difficult to produce. There is thus a need fornew methods of making such articles. The present invention addressesthat need.

SUMMARY

In some embodiments, the present invention relates to a method forproducing a jewelry article or a coated component of a jewelry article,comprising: (a) providing a jewelry article or a coated component of ajewelry article; (b) subjecting the jewelry article or coated componentof the jewelry article to a first layering process to obtain a firstcoated jewelry article or coated component of a jewelry articlecomprising a first coating; and (c) subjecting the first coated jewelryarticle or coated component of the jewelry article to a second layeringprocess to obtain a second coated jewelry article or coated component ofa jewelry article comprising a second coating. In further embodiments,the jewelry article or coated component of the jewelry article comprisesat least one of tungsten carbide, cobalt, tungsten, titanium, titaniumcarbide, zirconium, tantalum, rhodium, gold, silver, platinum,palladium, iridium, iron, stainless steel, 316 stainless steel, cobaltchrome, cobalt chromium, nickel, nitinol, aluminum, aluminum carbide,vanadium, ruthenium, copper, tungsten copper, brass, bronze, zinc, tin,German silver, niobium, molybdenum, rhenium, hafnium and combinationsand alloys of each of the foregoing. In still further embodiments, thefirst substrate is tungsten carbide. In additional embodiments, thefirst coating comprises at least one of a metal, a material havingmetallic properties, a metal compound, a metallic compound, a metalalloy, a metal carbide and a metal boride.

In some embodiments, the jewelry article is a ring, ornamental ring,engagement ring, toe ring, watch, watchcase, watchband, bracelet,necklace, pendant, charm, armlet, brocade, pin, clip, hairclip, fob,ornamental piercing, earring, nose ring, dog tag, amulet, banglebracelet, cuff bracelet, link bracelet, cuff link, key chain, moneyclip, cell phone charm, signet ring, class ring, friendship ring orpurity ring or a component thereof. In further embodiments, the firstcoating comprises at least one of titanium diboride (TiB₂), tungstencarbide, cobalt, tungsten, titanium, titanium carbide, zirconium,tantalum, rhodium, gold, silver, platinum, palladium, iridium, iron,stainless steel, cobalt chrome, cobalt chromium, nickel, nitinol,aluminum, aluminum carbide, vanadium, ruthenium, copper, brass, bronze,zinc, tin, German silver, niobium, molybdenum, hafnium, rhenium,chromium, a steel alloy, chromium carbide, zirconium carbide, tantalumcarbide, cobalt chrome molybdenum and combinations and alloys of each ofthe foregoing. In further embodiments, the first coating is chromium. Instill further embodiments, the first coating exhibits electricalconductivity. In additional embodiments, the first coating is depositedonto the substrate using vapor deposition, physical vapor deposition(PVD) or chemical vapor deposition (CVD).

In some embodiments, the second coating comprises at least one oftitanium nitride (TiN), titanium(2) nitride (Ti₂N), titaniumcarbo-nitride (TiCN), titanium-aluminum nitride (TiAlN),titanium-aluminum carbo-nitride (TiAlCN), chromium nitride (CrN),zirconium nitride (ZrN), chromium-titanium nitride (CrTiN),aluminum-titanium nitride (AlTiN), aluminum-titanium-chromium nitride(AlTiCrN), tungsten nitride (WN), titanium diboride (TiB₂), tungstencarbide, cobalt, tungsten, titanium, titanium carbide, zirconium,tantalum, rhodium, gold, silver, platinum, palladium, iridium, iron,stainless steel, cobalt chrome, cobalt chromium, nickel, nitinol,aluminum, aluminum carbide, vanadium, ruthenium, copper, brass, bronze,tungsten copper, zinc, tin, German silver, niobium, molybdenum, hafnium,rhenium, chromium, a steel alloy, gold nitride, silver nitride, aluminumnitride, vanadium nitride, tantalum nitride, chromium carbide, zirconiumcarbide, tantalum carbide, cobalt chrome molybdenum and combinations andalloys of each of the foregoing. In further embodiments, the secondcoating alters the luster of the jewelry article. In still furtherembodiments, the luster is selected from color change, adamantine, dull,greasy, metallic, pearly, resinous, silky, submetallic, vitreous, waxy,asterism, aventurescence, chatoyancy, and schiller. In additionalembodiments, the second coating exhibits electrical conductivity. Insome embodiments, the second coating is deposited onto the substrateusing electroplating, physical vapor deposition (PVD) or chemical vapordeposition (CVD). In further embodiments, the substrate is capable ofbeing manipulated prior to the first layering process. In still furtherembodiments, the manipulation is performed using at least one of a CNCmachine, a laser, photo lithography, a water jet, a lathe, a tumbler, adrill, a saw, a file, a tool, power tools and hand tools.

In some embodiments, the present invention relates to a coated jewelryitem or a coated component of a jewelry item having a plurality of metalor metallic layers, comprising: a jewelry item or a component of ajewelry item; a first coating comprising a metal, a metal compound, amaterial having metallic properties or a compound having metallicproperties, wherein the first coating is coupled to the jewelry item orthe component of the jewelry item; and a second coating comprising ametal, a metal compound, a material having metallic properties or acompound having metallic properties, wherein the second coating iscoupled to the first coating, and wherein the jewelry item or thecomponent of the jewelry item, the first coating and the second coatingform a surface that is resistant to deformation and wear. In furtherembodiments, the jewelry item or the component of the jewelry item, thefirst coating and the second coating form a surface that substantiallyretains the color of the second coating. In further embodiments, thejewelry item or the component of the jewelry item, comprises at leastone of tungsten carbide, cobalt, tungsten, titanium, titanium carbide,zirconium, tantalum, rhodium, gold, silver, platinum, palladium,iridium, iron, stainless steel, 316 stainless steel, cobalt chrome,cobalt chromium, nickel, nitinol, aluminum, aluminum carbide, vanadium,ruthenium, copper, tungsten copper, brass, bronze, zinc, tin, Germansilver, niobium, molybdenum, rhenium, hafnium and combinations andalloys of each of the foregoing. In still further embodiments, thejewelry item or the component of the jewelry item comprises tungstencarbide. In additional embodiments, the first coating comprises at leastone of a metal, a material having metallic properties, a metal compound,a metallic compound, a metal alloy, a metal carbide and a metal boride.In some embodiments, the first coating exhibits electrical conductivity.

In some embodiments, the first coating is deposited onto the jewelryitem or the component of the jewelry item, using vapor deposition,physical vapor deposition (PVD) or chemical vapor deposition (CVD). Infurther embodiments, the first coating comprises at least one oftitanium diboride (TiB₂), tungsten carbide, cobalt, tungsten, titanium,titanium carbide, zirconium, tantalum, rhodium, gold, silver, platinum,palladium, iridium, iron, stainless steel, cobalt chrome, cobaltchromium, nickel, nitinol, aluminum, aluminum carbide, vanadium,ruthenium, copper, brass, bronze, zinc, tin, German silver, niobium,molybdenum, hafnium, rhenium, chromium, a steel alloy, chromium carbide,zirconium carbide, tantalum carbide, cobalt chrome molybdenum andcombinations and alloys of each of the foregoing. In still furtherembodiments, the second coating comprises at least one of titaniumnitride (TiN), titanium(2) nitride (Ti₂N), titanium carbo-nitride(TiCN), titanium-aluminum nitride (TiAlN), titanium-aluminumcarbo-nitride (TiAlCN), chromium nitride (CrN), zirconium nitride (ZrN),chromium-titanium nitride (CrTiN), aluminum-titanium nitride (AlTiN),aluminum-titanium-chromium nitride (AlTiCrN), tungsten nitride (WN),titanium diboride (TiB₂), tungsten carbide, cobalt, tungsten, titanium,titanium carbide, zirconium, tantalum, rhodium, gold, silver, platinum,palladium, iridium, iron, stainless steel, cobalt chrome, cobaltchromium, nickel, nitinol, aluminum, aluminum carbide, vanadium,ruthenium, copper, brass, bronze, tungsten copper, zinc, tin, Germansilver, niobium, molybdenum, hafnium, rhenium, chromium, a steel alloy,gold nitride, silver nitride, aluminum nitride, vanadium nitride,tantalum nitride, chromium carbide, zirconium carbide, tantalum carbide,cobalt chrome molybdenum and combinations and alloys of each of theforegoing. In additional embodiments, the second coating alters theluster of the metallic substance. In some embodiments, the luster isselected from color change, adamantine, dull, greasy, metallic, pearly,resinous, silky, submetallic, vitreous, waxy, asterism, aventurescence,chatoyancy, and schiller. In further embodiments, the second coatingexhibits electrical conductivity. In still further embodiments, thesecond coating is deposited onto the substrate using electroplating,physical vapor deposition (PVD) or chemical vapor deposition (CVD). Inadditional embodiments, the first coating is selected from the groupconsisting of a metal, a material having metallic properties, a metalcompound, a metallic compound, a metal alloy, metal carbide and metalboride. In some embodiments, the second coating is selected from thegroup consisting of a metal, a material having metallic properties, ametal compound, a metallic compound, a metal alloy, metal carbide andmetal boride. In further embodiments, the second coating comprises atleast one of gold, silver, platinum, palladium, rhodium, ruthenium andan alloy of any of the foregoing. In still further embodiments, thesecond coating is a galvanic coating.

In some embodiments, the present invention further comprises washing thecoated jewelry article or the coated component of the jewelry article.In further embodiments, the coated jewelry article, coated component ofthe jewelry article or coated jewelry item exhibits a non-gray color orluster. In other embodiments, the coated jewelry article, coatedcomponent of the jewelry article or coated jewelry item substantiallyretain the color of the second coating. In still further embodiments,the jewelry article, component of the jewelry article or jewelry itemcomprises at least one of tungsten carbide, chrome, chromium, cobaltchrome or cobalt chromium. In additional embodiments, the coated jewelryarticle, coated component of the jewelry article or coated jewelry itemcomprises at least one layer of tungsten carbide, chrome, chromium,cobalt chrome or cobalt chromium. In some embodiments, the coatedjewelry article, coated component of the jewelry article or coatedjewelry item comprises at least one layer of steel, 316 stainless steel,nickel, nitinol, zirconium, cobalt, chrome, chromium, titanium-zirconium(TiZi), titanium-niobium-zirconium (TiNiZi) and an alloy of any of theforegoing. In further embodiments, the present invention relates to amethod for making a jewelry ring comprising a substrate, a first coatingof a metal, a material having metallic properties, a metal compound, ametallic compound, a metal alloy, metal carbide and metal boride, and anexternal metal or metallic coating, the method comprising cutting,pressing, molding, casting, striking, extruding, sintering and/orshaping the substrate into a ring shape; depositing the first coatingonto the substrate; and depositing the external metal or metalliccoating onto the first coating.

A method for making a jewelry ring comprising a substrate, a firstcoating of a metal, a material having metallic properties, a metalcompound, a metallic compound, a metal alloy and a metal carbide, and anexternal metallic coating is additionally provided. The method comprisescutting, pressing, molding, casting, striking, extruding, sinteringand/or shaping the substrate into a ring shape; depositing the firstcoating onto the substrate; and depositing the external metallic coatingonto the first coating.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a ring in accordance with an illustrative embodiment with atransverse cross-sectional cutout.

FIG. 2 shows a longitudinal cross-section of a ring in accordance withan illustrative embodiment.

FIG. 3 shows one embodiment of a chrome-steel (chromium-steel)composition of the second coating by component percentage.

FIG. 4 shows a comparison between the appearance of varying percentcompositions of chrome-steel (chromium-steel) alloys in the secondcoating of rings produced in accordance with the present disclosure, aswell as rings essentially comprising tungsten-carbide alloy (“classicTC”) or cobalt chrome alloy (“classic cobalt”).

FIG. 5 shows a schematic for producing a coated jewelry article inaccordance with an illustrative embodiment.

DETAILED DESCRIPTION

In a method for making a jewelry ring, according to the presentdisclosure, the cutting, pressing, molding, casting, striking,extruding, sintering and/or shaping of the substrate can utilize anyprocess known in the art, for example using a vacuum arc furnace, plasmahearth melting, induction skull melting, free smithing, wire electricdischarge machining (EDM), sink EDM, CNC lathe, and/or any polishing orengraving method known. Heat treatments may also be performed to impartdesired characteristics to the ring.

In various embodiments, the first coating is deposited onto thesubstrate by physical vapor deposition or chemical vapor deposition. Inadditional embodiments, the external metallic coating is deposited ontothe first coating using any known deposition technique, such as, forexample, vapor deposition, PVD or CVD. Where a hard surface is desired,for example for an article that is subject to extensive wear, such as aportion of a picture frame, a paperweight, or a portion of a piece offurniture (e.g., an inlay) that may be abraded during use, this processprovides a surface that is resistant to deformation and wear.

The present disclosure describes jewelry articles and coated componentsof jewelry articles as well as methods for producing the same. Thearticles and components produced in the context of the presentdisclosure advantageously comprise at least two coatings each comprisinga metal, metal alloy, metalloid or compound exhibiting metallic ormetalloid-like properties. In some embodiments, the first coatingdecreases the deformation and/or physical degradation of the jewelryarticle and/or coated component of a jewelry article. In someembodiments, the second coating advantageously increases the robustness,hardness and sustainability of the jewelry article and/or coatedcomponent of a jewelry article. In the context of the present invention,it is intended that the “hardness” of the jewelry article and/or coatedcomponent of a jewelry article may be determined using a standardmeasure for hardness, including but not limited to the Mohs scale ofhardness. See, e.g. Gupta, Chemical Metallurgy: Principles and Practice,Wiley-VCH, 2003.

The process is shown in FIG. 5. In accordance with the presentdisclosure, as shown in step 101, the articles and components are firstcleaned in a mild detergent solution with the aid of an ultrasoniccleaner to remove all grease and manufacturing residue. The articles andcomponents are then placed in a rack special designed for optimalexposure in a PVD machine. Specifically, the hooks affixed to the rackare designed such that they exhibit minimal contact with the insidesurface of the articles and components to avoid “shading,” a defect thatoccurs when the PVD substrate remains in the same location and the hookused to hold the substrate in covers or occludes that area from propercoverage of the deposition layer. As shown in step 103, the articles andcomponents are next run through a deposition process, such as a PVD orCVD process to deposit a first coating. In some embodiments, the methodsof the present disclosure utilize a dual layer PVD process, which uses amulti-target PVD machine that allows for uninterrupted movement from onedeposition layer to another without interruption of the vapor depositioncycle, which minimizes the risk of poor adhesion of the deposited filmto the substrate. In some embodiments, the first coating is a purechrome (chromium) deposit applied that measures approximately 0.1microns in thickness under a vacuum in an inert atmosphere, such asargon gas. As shown in step 105, the first coated articles andcomponents are next run through a second process, either a CVD, PVD orelectroplating process, the selection may depend, for example, on thematerials used, to deposit the second coating. In some embodiments, thesecond layer is applied during the second half of the PVD cycle as acobalt-chrome alloy (cobalt-chromium) deposition layer made up ofapproximately 60% cobalt, approximately 35% chrome and approximately 5%other compounds, including but not limited to carbon, manganese,silicon, phosphorus, sulfur, molybdenum, nickel and alloys thereof. Thesecond layer is deposited under an inert atmosphere at a thickness ofapproximately 0.2 microns. As shown in step 107, after deposition of thesecond coating the coated articles and components are removed from thePVD, CVD or electroplating equipment, and are then may be rinsed andpackaged.

The articles and components produced in accordance with the presentdisclosure may comprise varying percentages of metals, materials havingmetallic properties, metal and/or metallic compounds, metal alloys andmetal carbides. In some embodiments, as shown in FIG. 3 and FIG. 4, thearticles and components may comprise chrome:stainless steel(chromium:stainless steel) ratios including but not limited to 30:70,60:40, 70:30, 75:25, 80:20 and 90:10. In further embodiments, additionalcompounds, including but not limited to carbon, manganese, silicon,phosphorus, sulfur, molybdenum, nickel and alloys thereof, may comprisethe articles and components produced in accordance with the presentdisclosure. For example, a jewelry article comprising a chrome:stainlesssteel ratio of 90:10 may, in some embodiments, comprise about 0.003%carbon, about 0.2% manganese, about 0.1% silicon, about 0.005%phosphorus, about 0.003% sulfur, about 1.7% chrome (chromium), about0.25% molybdenum, about 1.2% nickel and about 6.5% iron.

Described herein are articles having two or more metallic coatings. Invarious embodiments, the first metallic coating provides a substrate fordepositing or electroplating the second, external metallic coating.

Particularly suitable external metallic coatings for these articles areany material that can be electroplated or vapor deposited onto the firstcoating. In some embodiments, the external metallic coating comprises amaterial that imparts an attractive coloration to the article, forexample platinum, rhodium, palladium, ruthenium, gold, a gold alloy,silver, a silver alloy, zirconium, tungsten nitride, tungsten carbide,or chrome or one of the materials described above. In particularembodiments, the external metallic coating modifies the luster of thearticle.

For example, one specific embodiment of a ring comprises a tungstencarbide substrate, a chromium first coating, and a rhodium externalmetallic coating.

The external metallic coating can be any coating appropriate for themetallic article. Where a hard surface is desired, for example for anarticle that is subject to extensive wear, such as a belt buckle, apicture frame, a paperweight, or a portion of a piece of furniture(e.g., an inlay) that may be abraded during use, the external metalliccoating can be a hard material such as TiAlN, TiN, or TiB₂. In otherembodiments, the external metallic coating comprises a material thatenhances the luster and/or imparts an attractive coloration to thearticle, including but not limited to titanium nitride (TiN),titanium(2) nitride (Ti₂N), titanium carbo-nitride (TiCN),titanium-aluminum nitride (TiAlN), titanium-aluminum carbo-nitride(TiAlCN), chromium nitride (CrN), zirconium nitride (ZrN),chromium-titanium nitride (CrTiN), aluminum-titanium nitride (AlTiN),aluminum-titanium-chromium nitride (AlTiCrN), tungsten nitride (WN),titanium diboride (TiB₂), tungsten carbide, cobalt, tungsten, titanium,titanium carbide, zirconium, tantalum, rhodium, gold, silver, platinum,palladium, iridium, iron, stainless steel, cobalt chrome, cobaltchromium, nickel, nitinol, aluminum, aluminum carbide, vanadium,ruthenium, copper, zinc, tin, German silver, niobium, molybdenum,hafnium, rhenium, chromium, a steel alloy, gold nitride, silver nitride,aluminum nitride, vanadium nitride, tantalum nitride, chromium carbide,zirconium carbide, tantalum carbide, cobalt chrome molybdenum andcombinations and allows of each of the foregoing.

FIGS. 1 and 2 provide a transverse cutout (FIG. 1) and a longitudinalcross-section (FIG. 2) of a finger ring 10 in accordance with someembodiments. In these embodiments, the substrate 12 is coated with afirst coating 14 and an external metallic coating 16. In the figures,the thicknesses of the first coating 14 and the external metalliccoating 16 are not necessarily drawn to scale.

Definitions

In the description herein, a number of terms are used. In order toprovide a clear and consistent understanding of the specification andclaims, the following definitions are provided:

As used herein, the singular forms “a”, “an” and “the” are intended toinclude the plural forms as well, unless the context clearly indicatesotherwise. Additionally, the use of “or” is intended to include“and/or”, unless the context clearly indicates otherwise.

Electroplating: Refers to the process of moving metal ions in solutionvia an electrical or conductive field to coat an object. This process isused for the deposition of a material, such as a metal or metal alloy,for imparting a desirable property onto the object, including but notlimited to resistance to scratching, corrosivity, chipping and dulling.

Jewelry: As used herein, “jewelry” refers to personal adornments wornfor ornament or utility. Jewelry includes but is in no way limited torings, ornamental rings, engagement rings, toe rings, watches,watchcases, bracelets, necklaces, chains, pendants, charms, armlets,brocades, pins, clips, hairclips, carved beads, fobs, ornamentalpiercings, earrings, nose rings, body jewelry, dog tags, amulets, banglebracelets, cuff bracelets, link bracelets, cuff links, tie clips, tiepins, tie tacks, key chains, money clips, cell phone charms, cutlerys,writing utensils, pens, charms, signet rings, class rings, friendshiprings or purity rings.

Layering: As used herein, “layering” refers to a process wherein acomposition, advantageously a metallic composition, is applied to asubstrate optionally comprising zero, one, or more layeredcomposition(s). In some embodiments, layering is performed using amachine or instrument capable of performing a vapor deposition orelectroplating process.

Luster: As used herein, “luster” refers to the way light interacts withthe surface and visual appearance of a substance. In some embodiments,the substance is a jewelry article. In further embodiments, thesubstance is a metallic substance that is optionally capable of beingmanipulated.

Manipulable: As used herein, a substance that is “manipulable” is onecapable of being patterned, surface modulated, etched, carved, faceted,cut, pressed, molded, cast, stricken, extruded, inlayed, shaped,polished, grinded, scraped, rubbed, sanded, buffed and/or filed. Inpreferred embodiments, the substance is a substrate for use in thepresent disclosure.

Metal Alloy: As used herein, a “metal alloy” is a mixture of two or moremetals or of substances with metallic properties. In some embodiments,metal alloys for use in the present disclosure comprise at least onetransition metal including but in no way limited to tungsten, cobalt,tungsten, titanium, zirconium, tantalum, aluminum, rhodium, gold,silver, platinum, palladium, iridium, iron, stainless steel, nickel,niobium, vanadium, ruthenium, copper, zinc, tin, molybdenum, hafnium andrhenium. In certain embodiments, the metal alloy is selected from a goldalloy, silver alloy, platinum alloy, palladium alloy and iron alloy. Infurther embodiments, a stainless steel alloy is selected from types18-8, 304 and 316.

Metal Carbide: A “metal carbide” is a compound comprising at least onetransition metal or substance with metallic properties and carbon orcarbon containing chemical group. In certain embodiments, metal carbidesfor use in the present disclosure include but are in no way limited totungsten carbide, tungsten-copper carbide, tungsten-silver-coppercarbide, titanium carbide, zirconium carbide, niobium carbide, hafniumcarbide, vanadium carbide, tantalum carbide, chromium carbide, aluminumcarbide and molybdenum carbide.

Metal Nitride: A “metal nitride” is a compound comprising at least onetransition metal or substance with metallic properties and nitrogen ornitrogen containing chemical group. In some embodiments, metal nitridesfor use in the present disclosure include but are in no way limited totitanium nitride, chromium nitride, zirconium nitride, tungsten nitride,gold nitride, silver nitride, aluminum nitride, vanadium nitride,tantalum nitride, aluminum-titanium-nitride, titanium-aluminum-nitrideand titanium-carbon-nitride.

Metal Salt: A “metal salt” is a compound comprising at least onecationic, transition metal or cation with metallic properties and ananion. In some embodiments, metal salts for use in the presentdisclosure comprise at least one transition metal including but in noway limited to tungsten, cobalt, titanium, zirconium, tantalum,aluminum, rhodium, gold, silver, platinum, palladium, iridium, iron,stainless steel, cobalt, chromium, aluminum, vanadium, ruthenium,copper, zinc, tin, nickel, niobium, molybdenum, rhenium and hafnium.

Metal Sulfide: A “metal sulfide” is a compound comprising at least onetransition metal or substance with metallic properties and sulfur orsulfur containing chemical group.

Polishing: As used herein, “polishing” refers to the process ofsmoothing and/or increasing the luster of a surface by the applicationof physical or chemical action or agent to a substance.

Vapor Deposition: Refers to a general process for the deposition ofcompounds onto a designated substrate. In preferred embodiments, the useof vapor deposition in the context of the present disclosure refers tochemical vapor deposition (CVD), physical vapor deposition (PVD), plasmaenhanced chemical vapor deposition (PECVD), diamond CVD coating, ionizedphysical vapor deposition (IPVD), sputtering and thermal evaporation. Incertain embodiments, vapor deposition is optionally used to add a firstand/or a second layer to a substrate used to produce a jewelry article.In preferred embodiments, the first and/or second layer comprises ametal coating comprising one or more of tungsten, cobalt, tungsten,titanium, zirconium, tantalum, aluminum, rhodium, gold, silver,platinum, palladium, iridium, iron, stainless steel, nickel, niobium,vanadium, ruthenium, copper, zinc, tin, hafnium, molybdenum and rhenium.In certain embodiments, the metal alloy is selected from a gold alloy,silver alloy, platinum alloy, palladium alloy and iron alloy. In furtherembodiments, a stainless steel alloy is selected from types 18-8, 304and 316.

Other embodiments within the scope of the claims herein will be apparentto one skilled in the art from consideration of the specification orpractice of the invention as disclosed herein. It is intended that thespecification be considered exemplary only, with the scope and spirit ofthe invention being indicated by the claims.

In view of the above, it will be seen that the several advantages of theinvention are achieved and other advantages attained.

As various changes could be made in the above methods and compositionswithout departing from the scope of the invention, it is intended thatall matter contained in the above description and shown in theaccompanying drawings shall be interpreted as illustrative and not in alimiting sense.

All references cited in this specification are hereby incorporated byreference. The discussion of the references herein is intended merely tosummarize the assertions made by the authors and no admission is madethat any reference constitutes prior art. Applicants reserve the rightto challenge the accuracy and pertinence of the cited references.

REFERENCES

The following references are incorporated herein by reference in theirentireties: U.S. Pat. Nos. 5,021,208; 6,062,045; 6,928,734.

The following references are also incorporated by reference herein intheir entirely: U.S. Pat. No. 6,544,315, title “Sintered Jewelry andDecorative Articles”; U.S. Pat. No. 6,553,667, titled “Apparatus andMethod for Manufacturing Composite Articles Including Wear ResistantJewelry and Medical and Industrial Devices and Composites Thereof”; U.S.Pat. No. 6,990,736, titled “Methods for Preparing Jewelry ArticlesComprising Sintered Tungsten Carbide”; U.S. Pat. No. 6,993,842, titled“Methods and Jewelry Articles Comprising Sintered Tungsten Carbide”;U.S. Pat. No. 7,032,314, titled “Methods of Making TungstenCarbide-Based Annular Jewelry Rings”; U.S. Pat. No. 7,076,972, titled“Tungsten Carbide-Based Annular Jewelry Article”; U.S. application Ser.No. 12/141,791, titled “Tungsten Ring Composition”; U.S. Pat. No.7,761,996, titled “Methods of Making Tungsten Carbide-Based AnnularJewelry Rings”; U.S. Pat. No. 8,061,033, titled “Methods of MakingTungsten Carbide-Based Annular Jewelry Rings”; U.S. Pat. App. Ser.61/492,197, filed Jun. 1, 2011; U.S. Pat. App. Ser. 61/493,283, filedJun. 3, 2011; U.S. patent application Ser. No. 13/152,226, filed Jun. 2,2011, titled “Multi-Coated Metallic Articles and Methods of MakingSame”; Dobkin et al., “Principles of Chemical Vapor Deposition,”Springer, New York (2003); and Mahan, “Physical Vapor Deposition of ThinFilms,” Wiley-Interscience, New York (2000).

1. An article comprising: a substrate; a first coating deposited overthe substrate, wherein the first coating comprises at least one of ametal, a metal compound, a material comprising a metallic property, ametallic compound, a metal alloy, or a compound comprising a metallicproperty; and an external metallic coating such that the externalmetallic coating is outermost, wherein the external metallic coatingcomprises at least one member from at least one of a first group or asecond group, wherein the first group comprises at least one ofchromium-titanium nitride (CrTiN), aluminum-titanium nitride (AlTiN),aluminum-titanium-chromium nitride (AlTiCrN), tungsten nitride (WN),tungsten carbide, tungsten, zirconium, cobalt chrome, cobalt chromium,nitinol, aluminum carbide, vanadium, copper, brass, bronze, tungstencopper, zinc, tin, German silver, niobium, molybdenum, hafnium,chromium, a steel alloy, silver nitride, aluminum nitride, vanadiumnitride, tantalum nitride, tantalum carbide, or cobalt chromemolybdenum, or any combination thereof, but excludes titanium carbide,titanium nitride, titanium boride, hafnium carbide, hafnium nitride,hafnium boride, zirconium carbide, zirconium nitride, zirconium boride,and stainless steel, wherein the second group comprises at least one ofcobalt, tantalum, iron, or nickel, wherein the second group excludestitanium carbide, titanium nitride, titanium boride, hafnium carbide,hafnium nitride, hafnium boride, zirconium carbide, zirconium nitride,zirconium boride, gold and platinum.
 2. A method for making an articlecomprising a substrate, a first coating comprising at least one of ametal, a metal compound, a material comprising a metallic property, ametallic compound, a metal alloy, or a compound comprising a metallicproperty, and an external metallic coating, the method comprising:forming the substrate into a desired shape; depositing the first coatingonto the substrate; and depositing the external metallic coating ontothe first coating such that the external metallic coating is outermost,wherein the external metallic coating comprises at least one member fromat least one of a first group or a second group, wherein the first groupcomprises at least one of chromium-titanium nitride (CrTiN),aluminum-titanium nitride (AlTiN), aluminum-titanium-chromium nitride(AlTiCrN), tungsten nitride (WN), tungsten carbide, tungsten, zirconium,cobalt, cobalt chrome, cobalt chromium, nitinol, aluminum carbide,vanadium, copper, brass, bronze, tungsten copper, zinc, tin, Germansilver, niobium, molybdenum, hafnium, rhenium, tantalum, chromium, asteel alloy, silver nitride, aluminum nitride, vanadium nitride,tantalum nitride, chromium carbide, tantalum carbide, cobalt chromemolybdenum, or any combination thereof, but excludes titanium carbide,titanium nitride, titanium boride, hafnium carbide, hafnium nitride,hafnium boride, zirconium carbide, zirconium nitride, zirconium boride,and stainless steel, wherein the second group comprises at least one ofcobalt, tantalum, iron, or nickel, wherein the second group excludestitanium carbide, titanium nitride, titanium boride, hafnium carbide,hafnium nitride, hafnium boride, zirconium carbide, zirconium nitride,zirconium boride, gold and platinum.
 3. The method of claim 2, whereinthe first coating is deposited onto the substrate by physical vapordeposition.
 4. The method of claim 2, wherein the external metalliccoating is deposited onto the first coating using electroplating, PVD orCVD.
 5. The method of claim 2, wherein the first coating is titaniumnitride (TiN), titanium(2) nitride (Ti₂N), titanium carbo-nitride(TiCN), titanium-aluminum nitride (TiAlN), titanium-aluminumcarbo-nitride (TiAlCN), chromium nitride (CrN), zirconium nitride (ZrN),chromium-titanium nitride (CrTiN), aluminum-titanium nitride (AlTiN),aluminum-titanium-chromium nitride (AlTiCrN), tungsten nitride (WN),titanium diboride (TiB₂), gold nitride, silver nitride, aluminumnitride, vanadium nitride or tantalum nitride.
 6. The method of claim 5,wherein the first coating is titanium nitride.
 7. The method of claim 2,wherein the external metallic coating further comprises platinum,rhodium, palladium, ruthenium, gold, a gold alloy, silver, a silveralloy, zirconium, tungsten nitride, tungsten carbide, chrome, cobalt,tungsten, titanium, titanium carbide, tantalum, iridium, iron, stainlesssteel, 316 stainless steel, cobalt chrome, cobalt chromium, nickel,nitinol, aluminum, aluminum carbide, vanadium, copper, tungsten copper,zinc, tin, German silver, niobium, molybdenum, rhenium, hafnium, alloysof each of the foregoing or any combinations thereof.
 8. The method ofclaim 2, wherein the external metallic coating comprises rhodium.
 9. Themethod of claim 6, wherein the external metallic coating comprisesrhodium.
 10. The method of claim 2, wherein the article is an item ofjewelry.
 11. The method of claim 10, wherein the item of jewelry is aring, pendant, dog tag, hairclip, chain, watchcase, pin, bracelet,necklace, earring, charm, ornamental ring, engagement ring, toe ring,watch, armlet, brocade, clip, fob, ornamental piercing, nose ring,amulet, bangle bracelet, cuff bracelet, link bracelet, cuff link, keychain, money clip, cell phone charm, signet ring, class ring, friendshipring or purity ring or a component any of the foregoing.
 12. The methodof claim 10, wherein the item of jewelry is a finger ring.